Methods for forming low temperature semiconductor layers and related semiconductor device structures

ABSTRACT

A method for forming a metal nitride film with good film closure at low temperatures is disclosed. The method may comprise utilizing plasma to form NH and NH2 radicals to allow for the formation of the metal nitride at low temperatures. The method may also comprise flowing an etch gas to result in an amorphous film with uniform thickness. The method may also comprise flowing an alkyl hydrazine to inhibit three-dimensional island growth of the metal nitride film.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

The present disclosure claims the benefit of U.S. Provisional Patent Application No. 62/514,585, filed on Jun. 2, 2017 and entitled “METHODS FOR FORMING LOW TEMPERATURE SEMICONDUCTOR LAYERS AND RELATED SEMICONDUCTOR DEVICE STRUCTURES,” which is incorporated herein by reference.

FIELD OF INVENTION

The present disclosure generally relates to methods for forming semiconductor layers at low temperatures. Particularly, the present disclosure relates to formation of thin nitride films, such as titanium nitride (TiN), for example. The nitride films are formed in a manner that results in a uniform film due to film closure.

BACKGROUND OF THE DISCLOSURE

Nitride films have been formed with many different processes. Some processes have resulted in formation of films through island growth. Island growth may comprise a process in which a plurality of separate film growths initiates, with empty areas between the separate film growths being filled in with subsequent time. The growth may take place as modeled by Volmer-Weber growth.

FIGS. 1A-1D illustrate a prior art process in which Volmer-Weber growth may take place. In FIG. 1A, a device 100 comprises a substrate 110 and a monolayer 120. The substrate 110 may comprise hafnium oxide, for example, while the monolayer 120 may comprise titanium nitride. The monolayer 120 may form initially by nucleation and may grow laterally in two dimensions. There may be a plurality of different monolayers 120 on the substrate 110.

In the next step of the Volmer-Weber growth, there may be a film growth in a third dimension on the monolayer 120 to form a peaked growth 130 as illustrated in FIG. 1B. The formation of the peaked growth 130 may be favorable due to an increase in surface energy of the peaked growths, a surface chemical termination, and a density of available reaction sites. FIG. 1C illustrates the situation where the monolayers 120 have been converted to the peaked growths 130 on top of the substrate 110.

The Volmer-Weber growth may continue such that the entirety of the substrate 110 is covered with peaked growths 150, as shown in FIG. 1D, such that a monolayer 140 of titanium nitride is formed. However, there may be difficulty encountered in trying to get the film growth to completely fill in the spaces. For example, in the Volmer-Weber growth model, the film growth may be closed no thinner than 15-20 Angstroms in the best case scenario. Film closure may not be possible for film thicknesses of less than 20 Angstroms.

As a result, it is desired to develop a method in which formation of a film is possible with closure to result in a uniform film. The method may apply to form either an amorphous film or a crystalline film.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

While the specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the invention, the advantages of embodiments of the disclosure may be more readily ascertained from the description of certain examples of the embodiments of the disclosure when read in conjunction with the accompanying drawing, in which:

FIGS. 1A, 1B, 1C and 1D illustrate a prior art process of film growth according to Volmer-Weber growth;

FIGS. 2, 3 and 4 illustrate a process for forming films in accordance with embodiments of the invention; and

FIGS. 5, 6 and 7 illustrate a process for forming films in accordance with embodiments of the invention.

It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

As used herein, the term “substrate” may refer to any underlying material or materials that may be used, or upon which, a device, a circuit or a film may be formed.

The embodiments of the disclosure may include methods for forming metal nitride films at low temperatures. The films formed may be amorphous films or crystalline films with a high degree of uniformity. The films formed may be continuous amorphous films. The films may be formed onto a substrate within a reaction chamber. It is an object of the invention to form amorphous films in a manner such that three-dimensional peaked growth or island growth, similar to those shown in FIGS. 1A-1D, may be avoided. Embodiments of the disclosure may include achieving good film closure for ultra-thin films, in the order of sub-nm films. The good film closure may be achieved in the production of sub-nm closed TiN films and pMOS multi-Vt tuning applications.

In one embodiment of the invention, a method of forming a metal nitride film is disclosed in FIG. 2. Films formed by the method may include titanium nitride (TiN), tungsten nitride (WN), hafnium nitride (HfN), niobium nitride (NbN), zirconium nitride (ZrN), tantalum nitride (TaN), and ternary films, such as titanium tantalum nitride (TiTaN), for example. The method may include a metal nitride subcycle 200 and an additional treatment subcycle 250. The method may also include a repeat cycle 300 of the metal nitride subcycle 200, a repeat cycle 310 of the optional treatment subcycle 250, or a repeat cycle 320 of the entire method.

FIG. 3 illustrates the metal nitride subcycle 200. The metal nitride subcycle 200 may comprise a metal halogen precursor step 210, an inert gas purge 220, a nitrogen-containing plasma precursor step 230, and an inert gas purge 240. The metal halogen precursor step 210 may include flowing or pulsing onto the substrate a metal halogen precursor, such as: titanium chloride (TiCl_(x)), titanium bromide (TiBr_(x)), titanium fluoride (TiF_(x)), titanium iodide (TiI_(x)), tungsten chloride (WCl_(x)), tungsten bromide (WBr_(x)), tungsten fluoride (WF_(x)), tungsten iodide (WI_(x)), niobium chloride (NbCl_(x)), niobium bromide (NbBr_(x)), niobium fluoride (NbF_(x)), tantalum chloride (TaCl_(x)), tantalum bromide (TaBr_(x)), tantalum fluoride (TaF_(x)), hafnium chloride (HfCl_(x)), hafnium bromide (HfBr_(x)), zirconium chloride (ZrCl_(x)), or zirconium bromide (ZrBr_(x)), for example. The inert gas purge 220 and the inert gas purge 240 may be optional, or may include flowing or pulsing an inert gas, such as argon, helium, krypton, or nitrogen, for example.

The metal nitride subcycle 200 may also include the nitrogen-containing plasma precursor step 230. In this step, plasma may be used to form NH or NH₂ radicals when flowing or pulsing nitrogen (N₂), hydrogen (H₂), ammonia (NH₃), hydrazine (N₂H₄), or tert-butyl hydrazine (C₄H₉N₂H₃) onto the substrate. The radicals may be formed remotely or in-situ. The radicals formed are highly reactive and allow for formation of the metal nitride onto the substrate at a low temperature. The temperature of the reaction chamber may be less than 300° C., less than 250° C., or less than 200° C. The pressure of the reaction chamber may be between 0.1 and 10 Torr, or between 1 and 5 Torr, or between 1 and 3 Torr.

The additional treatment subcycle 250 may be optional and may include an optional film anneal step 260 or an optional film etch step 270 as shown in FIG. 4. The optional film anneal step 260 may lead to film densification and potential crystallization. The optional film anneal step 260 may result in a smooth film, densification of the structure, and removal of impurities, resulting in a thinner film.

The optional film etch step 270 may comprise a thermal atomic layer etching step. The optional film etch step 270 may be used for those metal nitride films formed using hydrazine or hydrazine derivatives. During the etch step 270, an etch gas may be flowed, comprising: molybdenum chloride (MoCl₅), niobium chloride (NbCl₅), tungsten chloride (WCl₅), niobium fluoride (NbF₅), tantalum chloride (TaCl₅), or tantalum fluoride (TaF₅). The etch gas may have the ability to fully etch a thick metal nitride layer after over a hundred plus cycles.

The temperature of the reaction chamber during the optional film etch step 270 may be less than 500° C., less than 450° C., or less than 400° C. The pressure of the reaction chamber during the optional film etch step 270 may be between 0.1 and 10 Torr, or between 1 and 5 Torr, or between 1 and 3 Torr.

The film that results from the method illustrated in FIGS. 2-4 may have an amorphous quality with good film closure. For example, a TiN film with a closure less than 15 Angstroms may be formed. Embodiments of the method may also apply to form crystalline films with a closure less than 10 Angstroms.

In one embodiment of the invention, a method for forming the metal nitride film on the substrate is disclosed and illustrated in FIG. 5. The method may comprise an island formation step 400, an alkyl termination step 410, and a metal nitride formation step 420. Each of the steps in the method may be formed using atomic layer deposition (ALD) techniques and processes.

The island formation step 400 may result in nucleation growth of the metal nitride film at a number of different locations on the substrate, similar to the situation illustrated in FIG. 1A. With the island formation, there may be reaction sites on the islands as well as reaction sites (—OH terminated sites, for example) on the substrate. The island formation step 400 may comprise flowing of a metal halogen precursor and a nitrogen precursor, such as titanium chloride and ammonia, for example. The alkyl termination step 410 (shown in FIG. 6) may be used to allow for reaction sites on the islands to be terminated.

The alkyl termination step 410 may comprise a metal halogen precursor step 500, an inert gas purge step 510, an alkyl hydrazine precursor step 520, and an inert gas purge step 530. The metal halogen precursor step 500 may include flowing or pulsing onto the substrate a metal halogen precursor, such as: titanium chloride (TiCl_(x)), titanium bromide (TiBr_(x)), titanium fluoride (TiF_(x)), titanium iodide (TiI_(x)), tungsten chloride (WCl_(x)), tungsten bromide (WBr_(x)), tungsten fluoride (WF_(x)), tungsten iodide (WI_(x)), niobium chloride (NbCl_(x)), niobium bromide (NbBr_(x)), niobium fluoride (NbF_(x)), tantalum chloride (TaCl_(x)), tantalum bromide (TaBr_(x)), tantalum fluoride (TaF_(x)), hafnium chloride (HfCl_(x)), hafnium bromide (HfBr_(x)), zirconium chloride (ZrCl_(x)), or zirconium bromide (ZrBr_(x)), for example. The inert gas purge 510 and the inert gas purge 530 may be optional, or may include flowing or pulsing an inert gas, such as argon, helium, krypton, or nitrogen, for example.

The alkyl hydrazine precursor step 520 may comprise flowing or pulsing an alkyl hydrazine gas, such as one with a —CH₃ or —CH₂—CH₃ termination. Examples of alkyl hydrazine gases include: ethyl hydrazine (CH₃CH₂N₂H₃), diethyl hydrazine (C₄H₁₂N₂), tert-butyl hydrazine (C₄H₉N₂H₃), methyl hydrazine (CH₃NHNH₂), or dimethyl hydrazine ((CH₃)₂N₂H₂), for example. As a result of the alkyl termination step 410, reaction sites on the island growths may be closed off to further reaction (thus, preventing any three-dimensional upward growth on the islands), but there may still remain reaction sites available on the substrate. For example, use of an alkyl hydrazine precursor, may allow for a metal halide to react with reaction sites (comprising —OH groups), instead of newly formed methyl and ethyl terminations on reaction sites on the islands. Such a situation may decrease the upward three-dimensional growth and promote lateral two-dimensional growth.

The metal nitride formation step 420 may then be used to fill in the gaps between the islands. As illustrated in FIG. 7, the metal nitride formation step 420 may comprise a metal halogen precursor step 550, an inert gas purge 560, a nitrogen-containing plasma precursor step 570, and an inert gas purge 580. The metal halogen precursor step 550 may include flowing or pulsing onto the substrate a metal halogen precursor, such as: titanium chloride (TiCl_(x)), titanium bromide (TiBr_(x)), titanium fluoride (TiF_(x)), titanium iodide (TiI_(x)), tungsten chloride (WCl_(x)), tungsten bromide (WBr_(x)), tungsten fluoride (WF_(x)), tungsten iodide (WI_(x)), niobium chloride (NbCl_(x)), niobium bromide (NbBr_(x)), niobium fluoride (NbF_(x)), tantalum chloride (TaCl_(x)), tantalum bromide (TaBr_(x)), tantalum fluoride (TaF_(x)), hafnium chloride (HfCl_(x)), hafnium bromide (HfBr_(x)), zirconium chloride (ZrCl_(x)), or zirconium bromide (ZrBr_(x)), for example. The inert gas purge 560 and the inert gas purge 580 may be optional, or may include flowing or pulsing an inert gas, such as argon, helium, krypton, or nitrogen, for example.

The metal nitride formation step 420 may also include the nitrogen-containing plasma precursor step 570. In this step, plasma may be used to form NH or NH₂ radicals when flowing or pulsing nitrogen (N₂), hydrogen (H₂), ammonia (NH₃), or hydrazine (N₂H₄) onto the substrate. The radicals may be formed remotely or in-situ. The radicals formed are highly reactive and allow for formation of the metal chloride onto the substrate at a low temperature. The temperature of the reaction chamber may be less than 300° C., less than 250° C., or less than 200° C. The pressure of the reaction chamber may be between 0.1 and 10 Torr, or between 1 and 5 Torr, or between 1 and 3 Torr.

The film that results from the method illustrated in FIGS. 5-7 may have an amorphous quality with good film closure. For example, a TiN film with a closure less than 15 Angstroms may be formed. Embodiments of the method may also apply to form crystalline films with a closure less than 10 Angstroms.

In at least one embodiment of the invention, the methods described above may be used to form sub-nm closed TiN films. A greater coverage may be achieved by using t-Butyl Hydrazine during the alkyl hydrazine precursor step 520 rather than ammonia in the nitrogen plasma step 570. In addition, the greater coverage may be achieved by using t-Butyl Hydrazine at a temperature much lower than that of ammonia. For example, flowing t-Butyl Hydrazine at temperatures ranging between 250 and 325° C. may result in a greater Titanium coverage than that of Ammonia at temperatures 100 to 200 degrees ° C. greater.

According to at least one embodiment of the invention, TiN may be grown for a PMOS multi-Vt tuning application. This may be achieved by forming a stack comprising of at least hafnium oxide, titanium nitride, titanium carbide, and titanium nitride. A titanium nitride film may be formed using t-Butyl Hydrazine resulting in tuning with voltages ranging between 50-100 mV that can be achieved by depositing titanium nitride films with thicknesses ranging between 5-10 Angstroms.

The example embodiments of the disclosure described above do not limit the scope of the invention, since these embodiments are merely examples of the embodiments of the invention, which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combination of the elements described, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims. 

What is claimed is:
 1. A method of forming a semiconductor film at a low temperature comprising: performing a metal nitride subcycle, where the metal nitride subcycle comprises: flowing a metal halogen precursor on a substrate in a reaction chamber to react a portion of the metal halogen precursor with a surface of the substrate; flowing an inert gas on the substrate to remove an excess portion of the metal halogen precursor; flowing a nitrogen precursor on the substrate, the metal halogen precursor as reacted with the surface of the substrate reacting with a portion of the nitrogen precursor to form a metal nitride film on the substrate; and flowing an inert gas on the substrate to remove an excess portion of the the nitrogen precursor; wherein a temperature of the reaction chamber is less than 300° C., less than 250° C., or less than 200° C.
 2. The method of claim 1, further comprising a treatment subcycle comprising: annealing the metal nitride film; and etching the metal nitride film.
 3. The method of claim 2, wherein, during the etching of the metal nitride film, a temperature of the reaction chamber is less than 500° C., less than 450° C., or less than 400° C.
 4. The method of claim 2, wherein, during the etching of the metal nitride film, a pressure of the reaction chamber is between 0.1 and 10 Torr, between 1 and 5 Torr, or between 1 and 3 Torr.
 5. The method of claim 1, wherein the metal halogen precursor is at least one of: titanium chloride (TiCl_(x)), titanium bromide (TiBr_(x)), titanium fluoride (TiF_(x)), titanium iodide (TiI_(x)), tungsten chloride (WCl_(x)), tungsten bromide (WBr_(x)), tungsten fluoride (WF_(x)), tungsten iodide (WI_(x)), niobium chloride (NbCl_(x)), niobium bromide (NbBr_(x)), niobium fluoride (NbF_(x)), tantalum chloride (TaCl_(x)), tantalum bromide (TaBr_(x)), tantalum fluoride (TaF_(x)), hafnium chloride (HfCl_(x)), hafnium bromide (HfBr_(x)), zirconium chloride (ZrCl_(x)), or zirconium bromide (ZrBr_(x)).
 6. The method of claim 1, wherein the nitrogen precursor is at least one of: an alkyl hydrazine precursor or a nitrogen-containing plasma precursor.
 7. The method of claim 6, wherein the alkyl hydrazine precursor is at least one of: ethyl hydrazine (CH₃CH₂N₂H₃), diethyl hydrazine (C₄H₁₂N₂), tert-butyl hydrazine (C₄H₉N₂H₃), methyl hydrazine (CH₃NHNH₂), or dimethyl hydrazine ((CH₃)₂N₂H₂).
 8. The method of claim 6, wherein the nitrogen-containing plasma precursor is at least one of: nitrogen (N₂), hydrogen (H₂), ammonia (NH₃), or hydrazine (N₂H₄).
 9. The method of claim 1, wherein the metal nitride film forms a continuous amorphous film of uniform thickness.
 10. The method of claim 9, further comprising an alkyl termination step for terminating an ability of a reaction site on the series of separated islands to react.
 11. The method of claim 10, wherein the alkyl termination step comprises: flowing a metal halogen precursor; flowing an inert gas; flowing an alkyl hydrazine precursor, the metal halogen precursor reacting with the metal halogen precursor to close off reaction sites in the separated islands; and flowing the inert gas.
 12. The method of claim 1, wherein the inert gas comprises at least one of: argon, helium, krypton, or nitrogen.
 13. A semiconductor device, wherein the semiconductor device is formed by the method of claim
 1. 14. A method of forming a semiconductor film at a low temperature comprising: forming a plurality of metal nitride growths on the substrate as an island formation step, the island formation step comprising: flowing a metal halogen precursor on a substrate in a reaction chamber to react a portion of the metal halogen precursor with a surface of the substrate; flowing an inert gas on the substrate to remove an excess portion of the metal halogen precursor; flowing a nitrogen precursor on the substrate, the metal halogen precursor as reacted with the surface of the substrate reacting with a portion of the nitrogen precursor to form a metal nitride film on the substrate; and flowing an inert gas on the substrate to remove an excess portion of the nitrogen precursor; terminating a reactive site on the metal nitride growths on the substrate as an alkyl termination step, the alkyl termination step comprising: flowing a metal halogen precursor on the substrate in a reaction chamber to react a portion of the metal halogen precursor with the substrate; flowing an inert gas on the substrate to remove an excess portion of the metal halogen precursor; flowing an alkyl hydrazine precursor on the substrate, the metal halogen precursor as reacted with the surface of the substrate reacting with the alkyl hydrazine precursor; and flowing an inert gas on the substrate to remove an excess portion of the alkyl hydrazine precursor; and forming a metal nitride film on the substrate as a metal nitride formation step, the metal nitride formation step comprising: flowing a metal halogen precursor on a substrate in a reaction chamber to react a portion of the metal halogen precursor with the substrate; flowing an inert gas on the substrate to remove an excess portion of the metal halogen precursor; flowing a nitrogen-containing plasma precursor on the substrate, the metal halogen precursor as reacted with the surface of the substrate reacting with the nitrogen- containing plasma precursor to form a metal nitride film; and flowing an inert gas on the substrate to remove an excess of the nitrogen- containing plasma precursor; wherein a temperature of the reaction chamber may be less than 300° C., less than 250° C., or less than 200° C.
 15. The method of claim 14, wherein the metal halogen precursor is at least one of: titanium chloride (TiCl_(x)), titanium bromide (TiBr_(x)), titanium fluoride (TiF_(x)), titanium iodide (TiI_(x)), tungsten chloride (WCl_(x)), tungsten bromide (WBr_(x)), tungsten fluoride (WF_(x)), tungsten iodide (WI_(x)), niobium chloride (NbCl_(x)), niobium bromide (NbBr_(x)), niobium fluoride (NbF_(x)), tantalum chloride (TaCl_(x)), tantalum bromide (TaBr_(x)), tantalum fluoride (TaF_(x)), hafnium chloride (HfCl_(x)), hafnium bromide (HfBr_(x)), zirconium chloride (ZrCl_(x)), or zirconium bromide (ZrBr_(x)).
 16. The method of claim 14, wherein the alkyl hydrazine precursor is at least one of: ethyl hydrazine (CH₃CH₂N₂H₃), diethyl hydrazine (C₄H₁₂N₂), tert-butyl hydrazine (C₄H₉N₂H₃), methyl hydrazine (CH₃NHNH₂), or dimethyl hydrazine ((CH₃)₂N₂H₂).
 17. The method of claim 14, wherein the nitrogen-containing plasma precursor is at least one of: nitrogen (N₂), hydrogen (H₂), ammonia (NH₃), or hydrazine (N₂H₄).
 18. The method of claim 14, wherein the inert gas comprises at least one of: argon, helium, krypton, or nitrogen. 